Montmorillonite (Mnt)-based solid acids have a wide range of applications in catalysis and adsorption of pollutants. For such solid acids, the acidic characteristic often plays a significant role in these applications. The objective of the current study was to examine the effects of H 3 PO 4 -activation and supporting WO 3 on the textural structure and surface acidic properties of Mnt. The Mnt-based solid acid materials were prepared by H 3 PO 4 treatment and an impregnation method with a solution of ammonium metatungstate (AMT) and were examined as catalysts in the dehydration of glycerol to acrolein. The catalysts were characterized by nitrogen adsorption-desorption, powder X-ray diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy, scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), diffuse reflectance ultraviolet-visible (DR UV-Vis) spectroscopy, temperature programmed desorption of NH 3 (NH 3 -TPD), diffuse reflectance Fourier-transform infrared (DR FTIR) spectroscopy of adsorbed pyridine, and thermogravimetric (TG) analyses. The phosphoric acid treatment of Mnt created Brönsted and Lewis acid sites and led to increases in specific surface areas, porosity, and acidity. WO 3 species influenced total acidity, acid strength, the numbers of Brönsted and Lewis acid sites, and catalytic performances. A high turnover frequency (TOF) value (31.2 h −1 ) based on a maximal 60.7% yield of acrolein was reached. The correlation of acrolein yield with acidic properties indicated that the cooperative role of Brönsted and Lewis acid sites was beneficial to the formation of acrolein and a little coke deposition (<3.3 wt.%). This work provides a new idea for the design of solid acid catalysts with cooperative Brönsted and Lewis acidity for the dehydration of glycerol.
A microwave hydrothermal (MWH) method was used to deposit WO 3 onto ZrO 2 –Al 2 O 3 with various ZrO 2 contents to prepare hydrodesulfurization (HDS) catalysts with high WO 3 loading (23 wt%) close to industrial hydrotreating, for achieving high W dispersion and weak W-support interaction. The catalysts with the same WO 3 and ZrO 2 contents were prepared by a conventional impregnation (IM) method as reference. The effects of catalyst preparation methods and ZrO 2 contents on the catalyst property and dibenzothiophene HDS activity were investigated. The results show that the MWH method leads to highly dispersed octahedrally coordinated W species which are weakly linked on ZrO 2 –Al 2 O 3 and easy to be reduced; no bulk WO 3 crystallites are observed even at high ZrO 2 content (50 wt%). Therefore, it causes better sulfidation and shorter WS 2 slabs. Contrarily, the IM method induces W species to agglomerate into bulk WO 3 crystallites which are poorly dispersed and hard to be reduced, which is further aggravated by ZrO 2 . The HDS activity of the MWH-prepared catalysts significantly increases with ZrO 2 up to 40 wt% ZrO 2 . This catalyst shows 2 times higher rate constant and 1.64 times higher efficiency of HDS than the IM-prepared catalyst with the same ZrO 2 content. For the IM-prepared catalysts, the HDS activity slightly increases at small amount of ZrO 2 (10 wt%) and then decreases drastically.
Weifan Gao,Guichang Zhang,Xiaoping Zhang,Shaoqi Zhou,Zihao Wang
The catalytic capability of original carbon nitride (CN) is limited by a small specific surface area and high electron–hole recombination rate. In this study, WO3-loaded porous carbon nanosheets (MCA-CN/WO3) were synthesized by thermal treatment with melamine, cyanuric acid and WCl6. The MCA-CN/WO3could degrade 98% of the methylene blue (MB) within 30 min in the photo-Fenton-like process, displaying better catalytic activity than the original CN (30%), pure MCA-CN (63%) and original CN/WO3(87%). The results of photoluminescence and electrochemical impedance spectroscopy demonstrated that the Z-scheme heterojunction of MCA-CN/WO3inhibited the recombination of electrons and holes. In addition, the porous nanosheet structure accelerated the electron transfer and provided abundant active sites for MB degradation. A radical quenching experiment indicated that the Z-scheme heterojunction facilitated the decomposition of H2O2to produce1O2for MB degradation. The possible degradation pathways of MB were proposed.Keywords:photo-Fenton-like process;WO3-loaded porous carbon nitride nanosheet;Z-scheme heterojunction;MB degradation
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